CN103649212A - Pressure-sensitive adhesives with onium-epoxy resin crosslinking system - Google Patents

Pressure-sensitive adhesives with onium-epoxy resin crosslinking system Download PDF

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CN103649212A
CN103649212A CN201280030797.9A CN201280030797A CN103649212A CN 103649212 A CN103649212 A CN 103649212A CN 201280030797 A CN201280030797 A CN 201280030797A CN 103649212 A CN103649212 A CN 103649212A
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monomer
methyl
epoxy functionalized
multipolymer
epoxy
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CN103649212B (en
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W·S·马奥尼
A·L·韦克尔
L·R·克雷普斯基
B·N·加达姆
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3M Innovative Properties Co
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/062—Copolymers with monomers not covered by C08L33/06
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
    • C08G59/32—Epoxy compounds containing three or more epoxy groups
    • C08G59/3209—Epoxy compounds containing three or more epoxy groups obtained by polymerisation of unsaturated mono-epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
    • C09J133/04—Homopolymers or copolymers of esters
    • C09J133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
    • C09J133/062—Copolymers with monomers not covered by C09J133/06
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/28—Web or sheet containing structurally defined element or component and having an adhesive outermost layer
    • Y10T428/2852—Adhesive compositions
    • Y10T428/287—Adhesive compositions including epoxy group or epoxy polymer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Epoxy Resins (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

A pre-adhesive composition is described comprising an epoxy-functional (meth)acryloyl copolymer and epoxy resin, which when crosslinked using an ionic photoacid generator (PAG) provides a pressure-sensitive adhesive and pressure-sensitive adhesive articles having desirable properties.

Description

The pressure sensitive adhesive that comprises *-cross linking of epoxy resin system
Background technology
In fact, Pressuresensitive Tape is seen everywhere in family and working space.In it one of is the most simply constructed, Pressuresensitive Tape comprises tackiness agent and backing, and integral construction under use temperature for being clamminess, and only use the modest pressure just to adhere to the most multiple substrate to form bonding.In this way, Pressuresensitive Tape has formed complete self-contained type's bonding system.
According to the Pressuresensitive Tape council (Pressure-Sensitive Tape Council), known pressure-sensitive adhesives (PSA) has and comprises following characteristic: (1) powerful and lasting clinging power, (2) as long as just can adhere by the light pressure of finger, (3) there are enough abilities to remain on above adherend, (4) there are enough cohesive strengths, thereby can from adherend, peel off neatly.Found that the material playing one's part to the full as PSA comprises through design and prepares to show the polymkeric substance of required viscous-elastic behaviour, described viscous-elastic behaviour realizes desired clinging power, peel adhesion and shearing and keeps equilibrium of forces.PSA is characterised in that conventionally and for example, is clamminess under room temperature (20 ℃).PSA does not comprise only having viscosity or only can attach to certain surperficial composition.
Conventionally the testing method of using design to be used for measuring individually clinging power, adhesive power (stripping strength) and force of cohesion (shearing confining force) is assessed these requirements, the Adhesion and Adhesives Technology:An Introduction publishing in 2002 as A.V.Pocius You Hanse Gardner press (Hanser Gardner Publication) (Cincinnati, Ohio (Cincinnati, OH)) (adheres to and adhesive techniques: outline) specified in (the 2nd edition).These are measured to be combined and have formed through being commonly used to characterize the balance of the characteristic of PSA.
Along with the expansion that Pressuresensitive Tape is used for many years, it is harsher that performance requriements has become.For example, originally expection, for supporting the shearing hold facility of appropriate load in room temperature, is now increasing substantially aspect service temperature and load for many application.So-called high performance pressure sensitive adhesive tapes is for example, in high temperature (70 ℃) lower support load, to reach those of 10,000 minutes.Generally by crosslinked PSA, realize the shearing hold facility of increase, but necessary due diligence to keep high-caliber clinging power and adhesive power to keep the balance of afore-mentioned characteristics.
For acrylic adhesive, there are two kinds of main mechanism of crosslinkings: the interpolymerization of multifunctional ethylenic unsaturated group and other monomers, and by covalency or the ionomer of the functional monomer such as vinylformic acid.Another kind method be use UV linking agent (such as benzophenone that can copolymerization) or after the photocrosslinking agent (such as polyfunctional benzophenone and triazine) that adds.In the past, use multiple different material as linking agent, for example polyfunctional acrylic ester, methyl phenyl ketone, benzophenone and triazine.Yet above-mentioned linking agent has some shortcoming, these shortcomings comprise with lower one or more: high volatile volatile; Incompatible with some polymeric system; Produce corrodibility or toxic by-products; Produce less desirable color; Need independent light-sensitive compound to cause crosslinking reaction; And the height susceptibility to oxygen.The particular problem of electronic industry and wherein other application on PSA contacting metal surface is the generation of corrodibility or toxic by-products and the generation of less desirable color.
Summary of the invention
In brief, the invention provides a kind of crosslinkable that comprises epoxy functionalized (methyl) acrylic copolymer and epoxy resin (being pre-tackiness agent) composition, when itself and ionic light acid producing agent (PAG) are cross-linked, provide the contact adhesive composition with less above-mentioned shortcoming.Due to the acid that needs the light acid producing agent of less amount to cause producing small amount, thereby reduced, PSA fades and/or the possibility of sensitive substrate corrosion, therefore composition of the present invention for electronic industry and wherein other of PSA contacting metal surface purposes in applying be more acceptable.
In one embodiment, provide a kind of crosslinkable paste compound, it comprises: solute epoxy functionalized (methyl) acrylic copolymer, and it comprises: a plurality of mutually poly-monomer with pendant epoxies base unit; The solvent monomer component that comprises the free redical polymerization of at least one (methyl) alkyl acrylate monomer and epoxy functionalized (methyl) acryloyl monomer; Epoxy resin; With ionic light acid producing agent (PAG); The amount that wherein ionic light acid producing agent (PAG) is not more than 1 weight part with the total monomer/multipolymer content with respect to 100 weight parts is used.
In certain embodiments, epoxy functionalized (methyl) vinylformic acid solute multipolymer comprises mutually poly-monomer, and these gather mutually monomer and comprise: (methyl) acrylate of the non-tertiary alcohol of 85 to 99 weight parts; Epoxy functionalized (methyl) acryloyl monomer of 1 to 20 weight part; Sour official's energy ethylenically unsaturated monomers of 1 to 15 optional weight part; Non-sour official's energy polar monomer of 0.5 to 10 optional weight part; The vinyl monomer of 0.5 to 5 weight part optionally; Total monomer meter based on 100 weight parts in polymkeric substance.Cross-linkable composition also can comprise multifunctional (methyl) acrylate with respect to multipolymer 0.01 to 5 weight part of 100 weight parts.
The present invention also provides the pressure sensitive adhesive for example, making from cross-linkable composition as herein described (paste compound), and comprises for example pressure-sensitive adhesive article of the coating of this type of tackiness agent.Pressure sensitive adhesive of the present invention (crosslinked composition) provides required tackiness, peel adhesion and shearing to keep equilibrium of forces, and meet Dahlquist standard, under application of temperature (being generally room temperature) under 1Hz frequency the modulus of tackiness agent lower than 3 * 10 6dyne/cm.
In this application, " pre-tackiness agent " refers to that crosslinkable forms the mixture that comprises epoxy functionalized multipolymer, epoxy resin and PAG of pressure sensitive adhesive.
" paste compound " refers to the solution of solute (being total to) polymkeric substance in one or more solvent monomers, and said composition has 500 to 10,000cP viscosity at 22 ℃.
In this article, " (methyl) acryloyl " comprises (methyl) acrylate and (methyl) acrylamide.
In this article, " (methyl) vinylformic acid " comprises methacrylic acid and vinylformic acid.
In this article, " (methyl) acrylate " comprises methacrylic ester and acrylate.
Term " alkyl " means saturated or undersaturated straight chain, side chain, ring-type or multi-ring alkyl.Unless otherwise noted, hydrocarbyl group comprises maximum 30 carbon atoms conventionally, maximum 20 carbon atoms usually, and maximum 10 carbon atoms even more usually.This term is used for containing alkyl, thiazolinyl, alkynyl group, and cyclic group (for example alicyclic and aromatic group).
Term " assorted alkyl " means saturated or undersaturated straight chain, side chain, ring-type or multi-ring alkyl (except as otherwise noted, conventionally comprise maximum 30 carbon atoms), it has at least one chain that in the chain such as O, S or N heteroatoms replaces carbon atom or comprises the functional group such as amide group, ester group, urea groups, carbamate groups Huo Mi functional group.
Term " (mixing) alkyl " comprises alkyl and assorted alkyl.
In this article, " alkyl " comprises straight chain, side chain and cyclic alkyl group, and comprises the alkyl group of unsubstituted alkyl and replacement.Except as otherwise noted, described alkyl group comprises 1 to 20 carbon atom conventionally.The example of " alkyl " includes but not limited to methyl, ethyl, n-propyl, normal-butyl, n-pentyl, isobutyl-, the tertiary butyl, sec.-propyl, n-octyl, 2-octyl group, n-heptyl, ethylhexyl, cyclopentyl, cyclohexyl, suberyl, adamantyl and norcamphyl etc. as used herein.Except as otherwise noted, alkyl group can be monovalence or multivalence.
When a group exists in described formula while surpassing one time in this article, no matter whether explicitly point out, all select independently each group.For example, in formula, exist while surpassing a R group, select independently each R group.
Word " preferably " and " preferably " refer to the embodiment of the present invention that some beneficial effect can be provided in some cases.Yet in identical situation or other situations, other embodiment also can be preferably.In addition, the statement of one or more preferred embodiments is not implied to other embodiment are disabled, and be not intended to other embodiment to get rid of outside scope of the present invention.
All numerals suppose be in this article subject to term " about " modification and preferably by term " accurately ", modified.As used herein, about the amount recording, term " about " refer in the amount recording as measures and to a certain extent careful technician by the deviation matching with the target of measurement and the tolerance range of device for performing measurements of expection.
Foregoing invention content of the present invention is not intended to describe each embodiment disclosed in this invention or every kind of embodiment.Below describe more specifically exemplified with exemplary embodiment.In the application some places in full, by example list, provide guidance, the example can be used in multiple combination.Under each situation, cited list is as just representative group, and should not be understood to exclusiveness list.
Embodiment
The invention provides a kind of pre-binder composition that comprises epoxy functionalized (methyl) acryloyl multipolymer and epoxy resin, said composition provides pressure sensitive adhesive and the pressure-sensitive adhesive article with required character when using ionic light acid producing agent (PAG) crosslinked.Preferably, multipolymer be sour official can with epoxy functionalized.
Triazine crosslinked dose of chlorination is highly effective and reliable UV linking agent, and usually for the preparation of high-performance PS A.Their oxytolerants, have removing ability, and can under LOIHT irradiates, solidify (methyl) acrylic acid composition.Yet the existence of chlorination reagent can be expectation in electronic industry and other application (as medical belt).Therefore, in some cases, it is desired eliminating triazine crosslinked dose of chlorination.
The invention describes the new mode that a kind of PAG by use utmost point low levels and sour official energy and epoxy functionalized multipolymer (for example Isooctyl acrylate monomer/vinylformic acid/glycidyl methacrylate (IOA/AA/GMA) multipolymer) obtain high-performance PS A.Be not bound by theory, it is believed that the initial acid original position of PAG activates the oxirane ring in a polymer chain towards epoxide group and/or acidic group in another polymer chain, to produce cross-linked polymer.
When using optical energy irradiation, the chipping reaction of ionic light acid producing agent and discharge one or more Lewis or
Figure BPA00001817476000000518
acid molecule, open loop and the addition of these Journal of Molecular Catalysis pendant epoxies groups are crosslinked to form.Available light acid producing agent be heat-staple and not with the reacting of multipolymer generation thermal initiation, and be easy to dissolve or be dispersed in cross-linkable composition.Those of pKa value≤0 that preferred light acid producing agent is wherein initial acid.Light acid producing agent is known and can be with reference to K.Dietliker, Chemistry and Technology of UV and EB Formulation for Coatings, Inks and Paints, vol.III, SITA Technology Ltd., London, 1991 (K.Dietliker, chemistry and the technology of coating UV and EB allotment, ink and coating, III volume, London SITA technology company, 1991).Also can be with reference to Kirk-Othmer Encyclopedia of Chemical Technology, 4 thedition, Supplement Volume, John Wiley and Sons, New York, year, pp253-255 (Kirk-Othmer Chemical Engineering Technology encyclopedia, the 4th edition, augment volume, New York John's prestige border publishing company that founds a state, year, 253-255 page).
The positively charged ion that can be used as the cationic moiety of ionic light trigger of the present invention comprises organic
Figure BPA0000181747600000051
positively charged ion, for example U.S. Patent number 4,250,311,3,708,296,4,069,055,4,216,288,5,084,586,5,124,417,5,554, those that describe in 664, and this class description is incorporated herein by reference, comprise aliphatic series or aromatics IVA VIIA (CAS version) center
Figure BPA0000181747600000052
salt, preferably I-, S-, P-, Se-, N-He C-center
Figure BPA0000181747600000053
salt, for example, be selected from sulfur oxide
Figure BPA0000181747600000054
, iodine
Figure BPA0000181747600000055
, sulphur
Figure BPA0000181747600000056
, selenium , pyridine
Figure BPA0000181747600000058
, carbon
Figure BPA0000181747600000059
with
Figure BPA00001817476000000510
those, and I-He S-center most preferably
Figure BPA00001817476000000511
salt, for example, be selected from sulfur oxide
Figure BPA00001817476000000512
, diaryl iodine
Figure BPA00001817476000000513
, triaryl sulphur
Figure BPA00001817476000000514
, alkyl diaryl sulphur
Figure BPA00001817476000000515
, di alkylaryl sulphur
Figure BPA00001817476000000516
with trialkyl sulphur those, wherein " aryl " and " alkyl " as defined and have maximum four independent substituting groups of selecting.Substituting group on aryl or moieties is less than 30 carbon atoms and maximum 10 heteroatomss that are selected from N, S, non-peroxidation O, P, As, Si, Sn, B, Ge, Te, Se by preferably having.Example comprises hydrocarbyl group such as methyl, ethyl, butyl, dodecyl, tetracosyl, benzyl, allyl group, benzylidene, vinyl and ethynyl;-oxyl group such as methoxyl group, butoxy and phenoxy group; Alkyl mercapto groups is such as methyl mercapto and phenyl sulfydryl; Alkyl oxygen carbonyl group is methoxycarbonyl and phenyloxycarbonyl for example; Alkyl carbonyl group such as formyl radical, ethanoyl and benzoyl; Hydrocarbyl oxycarbonyl oxygen base group is as acetoxyl group and hexanaphthene carbonyl oxygen base; Alkyl carbonamido group is acetamido and benzoylamino for example; Azo; Boryl; Halo group such as chloro, bromo, iodo and fluoro; Hydroxyl; Oxo; Phenylbenzene arsyl; Phenylbenzene antimony base; Trimethylammonium germanium base; Trimethylsiloxy; With aromatic group for example cyclopentadienyl, phenyl, tolyl, naphthyl and indenyl.Utilize sulphur
Figure BPA0000181747600000061
salt, substituting group can be by dialkyl group or diaryl sulphur
Figure BPA0000181747600000062
positively charged ion further replaces; Such example is two (the phenylbenzene sulphur of Isosorbide-5-Nitrae-phenylene
Figure BPA0000181747600000063
).
The character of the counter anion in ionic PAG can affect speed and the degree of the positively charged ion addition polymerization of epoxide group.For example, the Chem.Mater. of J.V.Crivello and R.Narayan (chemical material), 4,692, (1992) have reported that the reactive order between normally used non-nucleophilic negatively charged ion is SbF 6 ->AsF 6 ->PF 6 ->BF 4 -.Negatively charged ion on reactive impact owing to three principal elements: the protonic acid that (1) produces or the acidity of Lewis acid, the degree of the ion pair separation in the positively charged ion chain that (2) increase and (3) negatively charged ion extract fluorochemical and the susceptibility of chain termination subsequently.Also can use B (C 6f 5) 4 -.
Available
Figure BPA0000181747600000064
salt comprises diazonium salt, for example aryl diazonium salts; Halogen salt, for example diaryl iodine salt; Sulphur
Figure BPA0000181747600000067
salt, for example triaryl sulphur
Figure BPA0000181747600000068
salt; Selenium salt, for example triaryl selenium salt; Sulfur oxide
Figure BPA00001817476000000611
salt, for example triaryl sulfur oxide
Figure BPA00001817476000000612
salt; And other kinds salt, for example triaryl
Figure BPA00001817476000000614
and arsenic
Figure BPA00001817476000000615
salt, and pyrans
Figure BPA00001817476000000616
with sulfo-pyrans salt.
Available ionic light acid producing agent comprises two (4-tert-butyl-phenyl) iodine
Figure BPA00001817476000000618
hexafluoro antimonate (derives from the FP5034 of Connecticut State Stirrat good fortune Hampford research company (Hampford Research Inc., Stratford, CT) tM), the mixture of the following: triaryl sulphur
Figure BPA00001817476000000619
salt (phenylbenzene (4-thiophenyl) phenyl sulphur
Figure BPA00001817476000000620
hexafluoro antimonate, two (4-(phenylbenzene sulphur
Figure BPA00001817476000000621
base) phenyl) sulfuration hexafluoro antimonate) (with Syna PI-6976 tMderive from the Synasia company (Synasia Metuchen, NJ) of New Jersey Mei Taqin), (4-methoxyphenyl) phenyl-iodide
Figure BPA00001817476000000622
fluoroform sulphonate, two (4-tert-butyl-phenyl) iodine
Figure BPA00001817476000000623
hexafluoro antimonate, two (4-tert-butyl-phenyl) iodine
Figure BPA00001817476000000624
hexafluoro antimonate, two (4-tert-butyl-phenyl) iodine hexafluorophosphate, two (4-tert-butyl-phenyl) iodine
Figure BPA0000181747600000072
tetraphenyl borate salts, two (4-tert-butyl-phenyl) iodine
Figure BPA0000181747600000073
tosylate, two (4-tert-butyl-phenyl) iodine
Figure BPA0000181747600000074
fluoroform sulphonate, ([4-(octyl group oxygen base) phenyl] phenyl-iodide
Figure BPA0000181747600000075
hexafluorophosphate), ([4-(octyl group oxygen base) phenyl] phenyl-iodide
Figure BPA0000181747600000076
hexafluoro antimonate), (4-cumyl) (4-aminomethyl phenyl) iodine
Figure BPA0000181747600000077
four (pentafluorophenyl group) borate is (with Rhodorsil2074 tMderive from the blue star organosilicon company limited (Bluestar Silicones, East Brunswick, NJ) of Brunswick, New Jersey east), two (4-aminomethyl phenyl) iodine
Figure BPA0000181747600000078
hexafluorophosphate is (with Omnicat440 tMderive from the IGM resin company (IGM Resins Bartlett, IL) of Illinois Charles Bartlett), 4-(2-hydroxyl-1-oxygen base in tetra-last of the ten Heavenly stems) phenyl] phenyl-iodide
Figure BPA0000181747600000079
hexafluoro antimonate, triphenyl sulphur
Figure BPA00001817476000000710
hexafluoro antimonate is (with CT-548 tMderive from Qitai Sci-Tech Co., Ltd. (Chitec Technology Corp.Taipei, Taiwan) of Taibei City, TaiwanTai Wantaibeishi), phenylbenzene (4-thiophenyl) phenyl sulphur
Figure BPA00001817476000000711
hexafluorophosphate, two (4-(phenylbenzene sulphur base) phenyl) two (hexafluorophosphate), phenylbenzene (4-thiophenyl) the phenyl sulphur of sulfuration
Figure BPA00001817476000000713
hexafluoro antimonate, two (4-(phenylbenzene sulphur
Figure BPA00001817476000000714
base) phenyl) sulfuration hexafluoro antimonate, and these triaryl sulphur the blend of salt is (with trade(brand)name Syna PI-6992 tMwith Syna PI-6976 tM(respectively for PF 6and SbF 6salt) derive from the Synasia company of New Jersey Mei Taqin.
Light acid producing agent is used to be enough to realize the amount of the required degree of crosslinking of multipolymer.Required degree of crosslinking can change according to bond property and film thickness.The amount that realizes the needed smooth acid producing agent of required degree of crosslinking will depend on the quantum yield (each absorbs the number of the acid release molecule of photon) of light acid producing agent, pKa, the perviousness of polymeric matrix, the wavelength of irradiation and the time length of acid, and temperature.In general, light acid producing agent is with total monomer/multipolymer 0.01 to 1 weight part with respect to 100 weight parts, and preferably the amount of 0.1 to 0.5 weight part is used.
Optionally, the photosensitizers or the photoaccelerators that have a light acid producing agent comprise within the scope of the invention.The use of photosensitizers or photoaccelerators has changed the wavelength sensitivity of the radiation-sensitive composition that adopts latent catalyst of the present invention and light acid producing agent.When light acid producing agent is not during strong absorption incident radiation, the use of photosensitizers or photoaccelerators is especially favourable.The use of photosensitizers or photoaccelerators has increased radiosensitivity, thereby allows shorter open-assembly time and/or use more low-energy source of radiation.Any photosensitizers or photoaccelerators are all available, as long as the triplet energies of photosensitizers or photoaccelerators is at least 30 kcal/mol.The example of this type of photosensitizers is at reference Steven L.Murov, Handbook of Photochemistry, Marcel Dekker Inc., N.Y., 27-35 (1973) (Steven L.Murov, photochemistry handbook, the 27-35 of New York Marcel moral Kerr Corp (1973)) in table 2-1, provide, and comprise U.S.4,985, those that describe in 340 people such as () Palazzotto, and this describes incorporated herein by reference.When existing, the weighing scale based on light acid producing agent, in practice of the present invention, photosensitizers used or the amount of photoaccelerators are generally being less than 10 % by weight and being preferably less than 1.0 % by weight of photosensitizers or photoaccelerators.
(methyl) acryloyl multipolymer comprises epoxide-functional monomer.Exemplary epoxy official can have following formula by (methyl) acryloyl monomer:
Figure BPA0000181747600000081
Wherein:
R 7for-H or C 1-C 4alkyl;
X 1for-NR 9-or-O-;
R 9for-H or C 1-C 4alkyl; And
R 8(mixing) hydrocarbyl group for epoxy group(ing) replacement.
Preferably, R 8the straight chain with oxyethane (epoxy) group, side chain, ring-type or the polynuclear hydrocarbon class of group based on 2 to 30 carbon.More preferably, R 8group comprises 3 to 10 carbon, as glycidyl methacrylate (GMA).Some embodiment comprise epoxycyclohexyl group, as (methyl) vinylformic acid 3,4-epoxycyclohexyl methyl esters and vinylformic acid 3-(2,3-glycidoxy) phenyl ester, 2-[4-(2,3-glycidoxy) phenyl]-2-(4-acryloxy-phenyl) propane, vinylformic acid 4-(2,3-glycidoxy) cyclohexyl, vinylformic acid 2,3-epoxy cyclohexyl, and can Ebecryl tMthe acrylic monoester of 3605 poly-(bisphenol-A diglycidylethers) purchased from the blue park of New Jersey Wood Qing Te industrial, and there is the R according to following formula 8material :-[(CH 2) 5c (O) O] n-CH 2-epoxycyclohexyl, wherein n is 0 to 10 and preferred 1-4.
In an available embodiment, epoxide-functional monomer derived from ethylene base dimethyl a word used for translation lactones reacts with hydroxyalkyl epoxy compounds, as shown in scheme 1:
Figure BPA0000181747600000091
R wherein 4for C 1-C 6alkylidene group.
Some preferred epoxy monomers have following formula:
Figure BPA0000181747600000092
Wherein:
R 10for (mixing) hydrocarbyl group, preferred hydrocarbyl group;
R 11for-H or C 1-C 4alkyl;
X 2for-NR 12-or-O-, and
R 12for-H or C 1-C 4alkyl.
Epoxy functionalized (methyl) acryloyl monomer is not more than the amount use of 20 weight parts with the total monomer content of epoxy functionalized (methyl) acrylic copolymer with respect to 100 weight parts.In certain embodiments, epoxy functionalized (methyl) acryloyl monomer is used with the amount of total monomer content 1 to 20 weight part of epoxy functionalized (methyl) acryloyl multipolymer with respect to 100 weight parts.Preferably, epoxide-functional monomer is used with the amount of total monomer 1 to 10 weight part with respect to 100 weight parts.
Except epoxide-functional monomer, multipolymer comprises other monomers, for example comprises (methyl) acrylate (that is, (methyl) acrylate monomer), sour official energy ethylenically unsaturated monomers, the second non-sour official's energy polar monomer and vinyl monomer.In addition, multifunctional (methyl) acrylate can be used in (methyl) acrylic copolymer, to provide extra crosslinked and adhesion characteristic to strengthen.
(methyl) acrylate monomer that can be used for preparing epoxy functionalized (methyl) acrylic copolymer is (methyl) acrylate of monomer non-tertiary alcohol, and this alcohol comprises 1 to 14 carbon atom, and preferably comprises average 4 to 12 carbon atoms.
The example that is suitable as the monomer of (methyl) acrylate monomer comprises the ester of acrylic or methacrylic acid and non-tertiary alcohol, described non-tertiary alcohol is for example ethanol, 1-propyl alcohol, 2-propyl alcohol, n-butyl alcohol, 2-butanols, 1-amylalcohol, 2-amylalcohol, 3-amylalcohol, 2-methyl-1-butene alcohol, 3-methyl-1-butanol, 1-hexanol, 2-hexanol, 2-methyl-1-pentene alcohol, 3-methyl-1-pentene alcohol, 2-ethyl-n-butyl alcohol, 3, 5, 5-trimethylammonium-1-hexanol, 3-enanthol, 1-octanol, sec-n-octyl alcohol, isooctyl alcohol, 2-ethyl-1-hexanol, 1-decanol, 2-propyl enanthol, DODECANOL, 1-, 1-tridecyl alcohol, 1-tetradecanol, geraniol, dihydro-citronellol etc.In certain embodiments, preferred (methyl) acrylate monomer is the ester of (methyl) vinylformic acid and butanols or isooctyl alcohol or its combination, but the combination of two or more different (methyl) acrylate monomers is also suitable.In certain embodiments, preferred (methyl) acrylate monomer be (methyl) vinylformic acid and derived from the ester of the alcohol (as sec-n-octyl alcohol, geraniol or dihydro-citronellol) of renewable source.
In certain embodiments, expectation is that (methyl) acrylate monomer component comprises high T gmonomer, has at least 25 ℃, and the T of preferred at least 50 ℃ g.As used herein, " the T of term monomer g" refer to the second-order transition temperature of the homopolymer being made by this monomer.The example of suitable high Tg monomer includes but not limited to tert-butyl acrylate, methyl methacrylate, β-dimethyl-aminoethylmethacrylate, isopropyl methacrylate, n-BMA, Propenoic acid, 2-methyl, isobutyl ester, the secondary butyl ester of methacrylic acid, Tert-butyl Methacrylate, methacrylic acid stearyl ester, phenyl methacrylate, cyclohexyl methacrylate, isobornyl acrylate, isobornyl methacrylate, benzyl methacrylate, vinylformic acid 3, 3, 5 3-methyl cyclohexanol esters, cyclohexyl acrylate, N-octyl acrylamide and propyl methacrylate or combination.T that can be based on forming monomer gand weight percent, with Fox equation, estimate the T of multipolymer g.
(methyl) acrylate monomer is used in the amount of common 85 to 99 weight parts of the total monomer based on 100 weight parts.Preferably, (methyl) acrylate monomer is used with the amount of 90 to 95 weight parts of the total monomer of 100 parts.Comprising high T gduring monomer, multipolymer can comprise maximum 30 weight parts of (methyl) acrylate monomer component of 85 to 99 weight parts, preferred maximum 20 weight parts.
(methyl) acrylic copolymer optionally also comprises sour official's energy ethylenically unsaturated monomers, and wherein acid functional group can be acid itself (as carboxylic acid), or a part can be its salt (as alkali metal carboxylate).Available sour official can ethylenically unsaturated monomers includes but not limited to be selected from following those: ethylenic unsaturated carboxylic acid, ethylenic unsaturated sulfonic acid, the unsaturated phosphonic acids of ethylenic and their mixture.The example of this compounds comprises and is selected from following those: vinylformic acid, methacrylic acid, methylene-succinic acid, fumaric acid, β-crotonic acid, citraconic acid, toxilic acid, oleic acid, (methyl) β-acryloxypropionic acid, methacrylic acid 2-sulphur ethyl ester, styrene sulfonic acid, 2-acrylamide-2-methylpro panesulfonic acid, vinyl phosphonate, and their mixture.
Due to its availability, the sour official of sour official's energy and epoxy functionalized (methyl) acrylic copolymer can be selected from ethylenic unsaturated carboxylic acid by ethylenically unsaturated monomers conventionally, i.e. (methyl) vinylformic acid.When even stronger sour of needs, sour official can comprise ethylenic unsaturated sulfonic acid, the unsaturated phosphonic acids of ethylenic by ethylenically unsaturated monomers, or their mixture.
When existing, sour official can use in the amount of common at least 1 weight part of total monomer content based on unmodified sour official's energy (methyl) acrylic copolymer of forming of 100 weight parts by ethylenically unsaturated monomers.Acid official energy ethylenically unsaturated monomers is not more than 15 weight parts conventionally with the total monomer content of 100 parts, and is conventionally not more than the amount use of 10 weight parts.In certain embodiments, the total monomer content meter of epoxy functionalized (methyl) acrylic copolymer based on 100 weight parts, the sour official of use 1 weight part to 15 weight part can ethylenically unsaturated monomers.
In certain embodiments, use non-sour official to prepare epoxy functionalized (methyl) acrylic copolymer by polar monomer.As used herein, term " polar monomer " does not comprise that sour official can ethylenically unsaturated monomers, and is called " non-sour official can polar monomer ".
The representative example of suitable non-sour official's energy polar monomer includes but not limited to (methyl) vinylformic acid 2-hydroxyl ethyl ester; NVP; N-caprolactam; Acrylamide; Single N-alkyl or two N-AAM; N-tert-butyl acrylamide; Dimethylaminoethyl acrylamide; N-octyl acrylamide; (methyl) vinylformic acid gathers (alkoxyalkyl) ester, comprises (methyl) vinylformic acid 2-(2-ethoxy ethoxy) ethyl ester, (methyl) vinylformic acid 2-ethoxy ethyl ester, (methyl) vinylformic acid 2-methoxy ethoxy ethyl ester, methacrylic acid 2-methoxyl group ethyl ester, polyethyleneglycol (methyl) acrylate and their mixture.Preferred polar monomer comprises those that are selected from (methyl) vinylformic acid 2-hydroxyl ethyl ester and NVP.
Non-sour official can polar monomer can be based on 100 weight parts the amount of total monomer content meter 0 to 10 weight part use.In certain embodiments, this type of monomer is used with the amount of at least 0.5 weight part of the total monomer content of 100 parts.In certain embodiments, this type of monomer is used with the amount that is not more than 5 weight parts of the total monomer content of epoxy functionalized (methyl) acrylic copolymer of 100 parts.
During use, can be used for vinylbenzene (for example, alpha-methyl styrene), vinyl halide that vinyl monomer in (methyl) acrylic copolymer comprises vinylbenzene, replacement, and their mixture.As used herein, term " vinyl monomer " does not comprise sour official's energy ethylenically unsaturated monomers, acrylate monomer and polar monomer.
Vinyl monomer can (methyl) acrylic copolymer based on the unmodified sour official of forming of 100 weight parts the amount of total monomer content meter 0 to 5 weight part use.In certain embodiments, this type of monomer is used with the amount of at least 1 weight part of the total monomer content of epoxy functionalized (methyl) acrylic copolymer of 100 parts.
Preferably, multipolymer does not comprise allyl ethers, vinyl ether or vinyl ester monomers unit.
In order to increase the cohesive strength of binder composition through coating, multifunctional (methyl) acrylate monomer can be mixed in the blend of polymerisable monomer and to be cross-linked contributing to.This compounds is usually called chemical cross-linking agent.Multifunctional (methyl) acrylate is specially adapted to slurry polymerisation.The example of available multifunctional (methyl) acrylate includes but not limited to two (methyl) acrylate, three (methyl) acrylate and four (methyl) acrylate, as 1,6-hexylene glycol two (methyl) acrylate, PEG two (methyl) acrylate, polyhutadiene two (methyl) acrylate, urethane two (methyl) acrylate and propoxylated glycerol three (methyl) acrylate, and their mixture.The amount of multifunctional (methyl) acrylate and kind depend on the customization that should be used for of binder composition.
Conventionally, if used, multifunctional (methyl) acrylate is less than the amount use of 5 weight parts with the total monomer content of epoxy functionalized (methyl) acrylic copolymer with respect to 100 weight parts.In certain embodiments, multifunctional (methyl) acrylate can be less than the amount existence of 1 weight part.In certain embodiments, this type of chemical cross-linking agent is used with the amount of at least 0.01 weight part.In certain embodiments, this type of chemical cross-linking agent is used with the amount of at least 0.05 weight part.In certain embodiments, cross-linked composition does not comprise multifunctional (methyl) acrylate.
The method of preparing epoxy functionalized (methyl) acrylic copolymer comprises a partly polymerization single polymerization monomer, to produce, comprises epoxy functionalized (methyl) acrylic copolymer of solute and the paste compound of polymer solvent monomer not.Partially polymerized provide epoxy functionalized (methyl) vinylformic acid solute polymkeric substance in the solvent monomer of one or more free redical polymerizations can application type solution.In general, PAG and epoxy resin are joined to partially polymerized composition, be then coated on the one-step polymerization of going forward side by side in suitable substrate.When being exposed to ultraviolet radiation, existing light trigger free radical makes solvent monomer polymerization, simultaneously the polymerization of the pendant epoxies group of PAG initiation epoxy resin and multipolymer and crosslinked.When using slurry polymerisation object space method, ionic light acid producing agent is used with the amount of the solute multipolymer with respect to 100 weight parts and solvent monomer 0.01 to 1 weight part.
Should be appreciated that slurry polymerisation method will produce " dead polymer " in initial radical polymerization; That is, the polymkeric substance of the non-free radical polymerization of complete polymerization.Subsequently, solvent monomer not radical polymerization be incorporated on existing solute multipolymer.When with PAG and epoxy resin compounding slurry, be further exposed to the radical polymerization of UV initiation solvent monomer to produce different multipolymers.Meanwhile, PAG causes the cationoid polymerisation of the pendant epoxies group (being produced by solvent monomer) of the epoxide group of epoxy resin, the pendant epoxies group of solute multipolymer and multipolymer.
Slurry methods provides the advantage that is better than solvent or solution polymerization process; Slurry methods obtains higher molecular weight.These higher molecular weight have increased the amount of chain entanglement, have therefore improved cohesive strength.In addition, for high molecule size polymkeric substance, the distance between cross-link bond can be larger, and this increases lip-deep degree of wetting.
A kind of cross-linkable composition is provided herein, and it comprises the component that comprises the solute polymkeric substance of a plurality of polymeric monomeric units with pendant epoxies group (or oxyethane) unit, epoxy functionalized (methyl) acryloyl monomer solvent monomer that comprises free redical polymerization and (methyl) alkyl acrylate monomer (optional described other unreacted solvent monomers); Light trigger; Epoxy resin, PAG and optional multifunctional (methyl) acrylate chemistry linking agent.
Polymerization does not preferably exist such as please the carrying out under condition of the solvent of ethyl acetate, toluene and tetrahydrofuran (THF), and the functional group of the component of these solvents and paste compound not reaction solvent affects that different monomers is attached to speed in polymer chain and conventionally because polymer gel or the precipitation of solution causes lower molecular weight.
Can realize by paste compound being exposed to energy in the situation that there is light trigger the polymerization of (methyl) acrylate solvent monomer.In the situation that for example carrying out initiated polymerization with ionizing rays, also may not need energy activated initiator.Conventionally, with respect to the solvent monomer of unmodified epoxy functionalized (methyl) acrylic copolymer of 100 weight parts, light trigger can at least 0.0001 weight part, preferred at least 0.001 weight part, and more preferably the concentration of at least 0.005 weight part is used.Conventionally, with respect to the total monomer content of 100 weight parts, light trigger can be no more than 3.0 weight parts, is preferably no more than 1.0 weight parts, more preferably no more than the concentration of 0.5 weight part, uses.
The preferred method of preparing paste compound is light-initiated radical polymerization.The advantage of light polymerization process is 1) do not need to heat monomer solution, and 2) when turning off excitation light source, light-initiatedly stop completely.Can reach the polymerization of the viscosity that can be coated with, making monomer is maximum approximately 30% to the transformation efficiency of polymkeric substance.When reaching required transformation efficiency and viscosity, by removing light source and passing into air (oxygen) by bubbling in solution, with quencher, propagate free radical, thereby stop polymerization.Can in non-solvent monomer, prepare in the usual way solute polymkeric substance and proceed to high transformation efficiency (polymerization degree).When using solvent (monosomy or non-monosomy), can be except desolventizing (for example, by vacuum distilling) before or after forming paste compound.Although this operation is acceptable method, functional polymer's this operation that relates to high-degree of conversion is not preferred, because need extra solvent removal step, may need another material (non-monosomy solvent), and the dissolving of the solute polymkeric substance of high molecular and high-degree of conversion in monomer mixture may need considerable time.
Available light trigger comprises benzoin ether, as benzoin methyl ether and benzoin isopropyl ether; The methyl phenyl ketone replacing is for example with trade(brand)name IRGACURE651 or ESACUREKB-1 light trigger ((the Sartomer Co. of Sartomer company of Pennsylvania's west chester, West Chester, PA)) 2 of acquisition, 2-dimethoxy-2-phenyl methyl phenyl ketone light trigger, and dimethyl hydroxyl methyl phenyl ketone; The α-one replacing, as 2-methyl-2-hydroxypropiophenonepreparation; Aromatics SULPHURYL CHLORIDE, as 2-naphthalene-SULPHURYL CHLORIDE; With photosensitivity oxime, as 1-phenyl-1,2-propanedione-2-(O-oxyethyl group-carbonyl) oxime.In the middle of these, particularly preferably be the methyl phenyl ketone of replacement.
Preferred light trigger is can carry out Norrish I cracking to produce the light-sensitive compound of free radical, and described free radical can be by causing the addition of the two keys of acrylic acid series.Can light trigger be joined to mixture to be coated after multipolymer forms, light trigger can be joined to paste compound.This type of polymerizable photoinitiator is for example at United States Patent (USP) 5,902, in 836 and 5,506,279 people such as () Gaddam, describes to some extent.
Can irradiate paste compound and light trigger with polymerization single polymerization monomer component with the UV radiation activating.UV light source can have two types: 1) light source of relatively low light intensity is as backlight, and it provides and be generally 10mW/cm in the wavelength region of 280 nanometer to 400 nanometers 2or lower light intensity (is measured according to the method for USA National Institute of Standard and Technology (United States National Institute of Standards and Technology) approval, for example use electronic instrument and (the Electronic Instrumentation & amp Technology of technology company of Virginia Stirling, Inc. (Sterling, VA) the UVIMAP UM365L-S radiometer measurement of producing), with 2) the strong light source of high light is as medium pressure mercury lamp, and it provides usually above 10mW/cm 2, preferably 15 to 450mW/cm 2light intensity.Utilizing actinic radiation wholly or in part during polymeric size composition, high strength and short open-assembly time are preferred.For example, can successfully adopt 600mW/cm 2intensity and the open-assembly time of approximately 1 second.The scope of intensity can be 0.1 to 150mW/cm 2, preferably 0.5 to 100mW/cm 2, more preferably 0.5 to 50mW/cm 2.With respect to the total monomer content of unmodified sour official's energy (methyl) acrylic copolymer of forming of 100 weight parts, this light trigger preferably exists with the amount of 0.1 to 1.0 weight part.Therefore,, when the optical extinction coefficient of light trigger is low, can obtain relatively thick coating.
As previously mentioned, can monitor transforming degree by measure the specific refractory power of polymerisation medium between the light period.Available dope viscosity is with maximum 30%, and preferably 2% to 20%, more preferably 5% to 15%, the transformation efficiency in 7% to 12% scope (being the per-cent of the monomer of available polymerization) and obtaining most preferably.The molecular weight of solute polymkeric substance (weight average) is at least 100,000, preferably at least 500,000.
When preparation epoxy functionalized (methyl) as herein described acrylic copolymer, advantageously at the temperature lower than 70 ℃ (preferably 50 ℃ or lower), to be less than 24 hours, preferably be less than 12 hours, and the reaction times that is more preferably less than 6 hours proceeds in fact light-initiated polyreaction to complete, and monomer component exhausts.These temperature ranges and speed of reaction avoid needing radical polymerization inhibitor, wherein usually described radical polymerization inhibitor are joined in acrylic acid series system so that acrylic acid series stable system and do not occur less desirable premature polymerization and gelation.In addition, inhibitor add increase foreign matter, described foreign matter will remain in system, and suppress the required polymerization of paste compound and the formation of crosslinked pressure sensitive adhesive.Under 70 ℃ or higher processing temperature, continue to be greater than the reaction times of 6 to 10 hours, usually need radical polymerization inhibitor.
Composition also comprises epoxy resin.Suitable epoxy resin comprises and can be aliphatic series, alicyclic, aromatics or the monomer of heterocycle or oligomeric epoxy compounds.These materials are on average have >=1 polymerisable epoxide group of each molecule conventionally.Each molecule of some epoxy resin has >=1.5 or >=2 polymerisable epoxide groups.Oligomeric epoxide can be (for example has epoxy-terminated linear oligomer, the diglycidylether of polyoxyalkylene diols), the oligopolymer that has a framework epoxy unit (for example, polyhutadiene polyepoxide) or there is the oligopolymer (for example, glycidyl methacrylate oligopolymer or co-oligomer) of pendant epoxies group.Epoxide can be pure compound, or can be each molecule and comprise one, the mixture of the compound of two or more epoxide groups.Any suitable substituting group that these can have the main chain of any type and substantially not hinder cationic curing containing the material of epoxy group(ing).The exemplary substituting group of allowing comprises halogen, ester group, ether, sulfonate group, siloxane groups, nitryl group, phosphate groups etc.The molecular-weight average that contains the material of epoxy group(ing) can be about 58g/ mole to about 1000g/ mole or larger.
Available epoxy resin comprises the glycidyl ether compound of formula IV
Figure BPA0000181747600000161
R wherein 1for (mixing) hydrocarbyl group, and m is 1 to 6.R 1can be r, aliphatic group, aromatic group, or their combination.Exemplary loop oxide compound is the glycidyl ether of polyphenol, and it can be reacted by polyphenol and obtain (for example, 2,2-two-diglycidylether of (2,3-glycidoxy phenol)-propane) with the excessive chloroethanol such as epoxy chloropropane.The other example of this type of epoxide is in U.S. Patent No. 3,018,262 and at Handbook of Epoxy Resins, Lee and Neville, McGraw-Hill Book Co., New York (1967) (epoxy resin handbook, Lee and Neville, McGraw-hill plot book company, New York (1967)) in describe to some extent.
Can use much commercially available epoxy resin.Specifically, the epoxide being easy to get comprises the resin of epoxy octadecane, epoxy chloropropane, Styrene oxide 98min., oxyethylene group tetrahydrobenzene, Racemic glycidol, glycidyl methacrylate, the diglycidylether of dihydroxyphenyl propane (for example, derives from the EPON828 of Mai Tu specialty chemicals company (Momentive Specialty Chemicals), EPON825, EPON1004 and EPON1001) and the DER221 that derives from available Dow Chemical (Dow Chemical Co., Midland, MI), DER332 and DER334), vinyl cyclohexene dioxide (for example, deriving from the ERL4206 of Union Carbide Corporation (Union Carbide)), 3,4-epoxycyclohexyl methyl-3,4-oxirane ring hexene carboxylicesters (for example, derives from the ERL4221 of Union Carbide Corporation, CYRACURE UVR6110 and CYRACURE UVR6105), 3,4-epoxy-6-methyl cyclohexane ylmethyl-3,4-epoxy-6-methyl-cyclohexyl olefinic carboxylic acid ester (for example, deriving from the ERL4201 of Union Carbide Corporation), two (3,4-epoxy-6-methyl cyclohexane ylmethyls) adipic acid ester (for example, ERL4289), two (2,3-oxirane ring amyl groups) ether (for example, ERL0400), aliphatic epoxy resin (for example, ERL4050 and ERL4052) by polypropylene glycol modified, Dipentenedioxide (for example, ERL4269), epoxidized polybutadiene (for example, deriving from the OXIRON2001 of FMC Corp. (FMC Corp.)), the silicone resin that comprises epoxy-functional, flame retardant epoxy resin, for example brominated bisphenol type epoxy resin is (for example, DER580), the BDDE of resol (for example, deriving from DEN431 and the DEN438 of Dow Chemical), resorcinol diglycidyl ether (for example, deriving from the KOPOXITE of Ke Baisi company limited (Koppers Company, Inc.)), two (3,4-epoxycyclohexyl methyl) adipic acid ester (for example, ERL4299 or CYRACURE UVR6128), hexanaphthene--diox (for example, ERL-4234) for 2-(3,4-epoxycyclohexyl-5,5-spiral shell-3,4-epoxy), one ethylene oxide cyclohexene, 1,2-epoxy n-Hexadecane (for example, CYRACURE UVR-6216), alkyl glycidyl ether is alkyl Cs-C10 glycidyl ether (for example, deriving from the HELOXY MODIFIER7 of remarkable with keen determination Products Co., Ltd (Resolution Performance Products)) for example, alkyl C 12-C 14glycidyl ether (for example, derive from the HELOXY MODIFIER8 of Mai Tu specialty chemicals company), butylglycidyl ether (for example, HELOXY MODIFIER61), cresyl glycidyl ether (for example, HELOXY MODIFIER62), to tert-butyl-phenyl glycidyl ether (for example, HELOXY MODIFIER65), polyfunctional glycidyl ether is as 1, the diglycidylether of 4-butyleneglycol (for example, HELOXY MODIFIER67), the diglycidylether of neopentyl glycol (for example, HELOXY MODIFIER68), the diglycidylether of hexamethylene dioxane dimethanol (for example, HELOXY MODIFIER107), trimethylolethane trimethacrylate glycidyl ether (for example, HELOXY MODIFIER44), trihydroxymethylpropanyltri diglycidyl ether (for example, HELOXY48), the polyglycidyl ether of aliphatic polyol (for example, HELOXY MODIFIER84), polyoxyethylene glycol diepoxide (for example, HELOXY MODIFIER32), Bisphenol F epoxide (for example, derive from EPON862 and Araldite GY-281 that Hensel steps advanced material company (Huntsman Advanced Materials)), and 9, 9-is two, and [4-(2, 3-glycidoxy)-phenylfluorone (for example deriving from the EPON1079 of Mai Tu specialty chemicals company).
Other available materials containing epoxy group(ing) comprise those that comprise epoxy cyclohexane group, for example epoxycyclohexane carboxylate, typical case are as 3,4-epoxycyclohexyl methyl-3,4-epoxycyclohexane carboxylate, 3,4-epoxy-2-methyl cyclohexane ylmethyl-3,4-epoxy-2-methylcyclohexanecarboxylic acid ester and two (3,4-epoxy-6-methyl cyclohexane ylmethyl) adipic acid ester.The more detailed list of epoxy available compound of this character is at U.S.3, shown in 117,099 (people such as Proops).
Other available epoxy resin are well-known and for example comprise, for example, for example, such as epoxy chloropropane, alkylene oxide (propylene oxide), Styrene oxide 98min., alkylene oxide (butadiene oxide) and glycidyl esters (ethyl glycidyl ester).Also have some available epoxy resin to comprise epoxy functionalized organosilicon, for example, at U.S.4, those described in 279,717 people such as () Eckberg, commercially available from General Electric Corporation (General Electric Company).These epoxy resin are polydimethylsiloxanes, and wherein the Siliciumatom of 1 to 20 % by mole is replaced by epoxy alkyl group (preferably, epoxycyclohexyl ethyl, as U.S.5, described in 753,346 people such as () Leir).
Also can utilize the blend of the multiple material containing epoxy group(ing).Suitable blend can comprise the compound containing epoxy group(ing) that two or more weight-average molecular weight distribute, for example low-molecular-weight epoxide (for example weight-average molecular weight is lower than 200g/ mole), intermediate molecular weight epoxide (for example weight-average molecular weight approximately 200 to the scope of 1000g/ mole) and higher molecular weight epoxide (for example weight-average molecular weight is higher than about 1000g/ mole).Alternatively or in addition, epoxy resin can comprise and has such as the different chemical character of aliphatic series and aromatics or such as the blend of the material that contains epoxy group(ing) of polarity and nonpolar different functional groups.If needed, can mix extraly other cationoid reaction polymkeric substance (such as vinyl ether etc.).
In certain embodiments, crosslinkable binder composition comprises the epoxy resin with respect to epoxy functionalized multipolymer 0.1 to 10 weight part of 100 weight parts.Preferably, the epoxy resin that binder composition comprises 1 to 5 weight part.
The crosslinking copolymers that UV causes can scheme 1 and 2 below shown in.Show ester, epoxy group(ing) and optional acid mono unit, wherein subscript x, y and z are corresponding to the weight part of each monomeric unit.It is believed that between the optional side acid groups of the pendant epoxies group of epoxy functionalized multipolymer, the epoxide group of epoxy resin and epoxy functionalized multipolymer and have complicated reaction mechanism.
It is believed that between the pendant epoxies group of epoxy functionalized multipolymer and the pendant epoxies group of epoxy resin and have main cross-linking mechanism, as shown in scheme 1.In scheme 1, show sour official can and epoxy functionalized copolymer 1 a, it has (methyl) acrylate monomeric units, optional acid functional monomer unit and epoxide-functional monomer unit.Copolymer 1 a has a plurality of polymeric monomeric unit x, y and z, and they are corresponding to the weight part of each monomeric unit as previously mentioned.Unshowned is non-sour official's energy polar monomer unit, vinyl monomer unit or multifunctional (methyl) acrylate monomeric units.When using optical energy irradiation, the chipping reaction of ionic light acid producing agent and discharge one or more Lewis or acid molecule, the open loop of these Journal of Molecular Catalysis pendant epoxies groups and addition are to form oxygen functional polymer.The epoxy group(ing) of activation can through type IV epoxy resin (or epoxy resin of other descriptions) and open loop to form intermediate 5.Intermediate 5 can continue cationoid polymerisation from the adjacent ring oxygen groups of multipolymer or epoxy resin.
Or, from the initial acid of PAG, also can make the epoxy group(ing) proton of epoxy resin, then these side oxygen groups are by the pendant epoxies base open loop from multipolymer.As shown, the additional ring oxygen groups (m-1 illustrates with subscript) of epoxy resin can react and pass through cationoid polymerisation with adjacent ring oxygen groups.Should be further understood that the multipolymer that (methyl) acrylate copolymer illustrating can be initial solute multipolymer or the radical polymerization of the solvent monomer that caused by secondary UV produces.
Scheme 1
Alternatively, multipolymer can be cross-linked as shown in scheme 2 below.In scheme 2, show two kinds of sour officials can and epoxy functionalized copolymer 1 a and 1b, it has (methyl) acrylate monomeric units, optional acid functional monomer unit and epoxide-functional monomer unit.Copolymer 1 a and 1b have a plurality of polymeric monomeric unit x, y and z, and they are corresponding to the weight part of each monomeric unit as previously mentioned.Unshowned is non-sour official's energy polar monomer unit, vinyl monomer unit or multifunctional (methyl) acrylate monomeric units.When using optical energy irradiation, the chipping reaction of ionic light acid producing agent and discharge one or more Lewis or
Figure BPA0000181747600000202
acid molecule, the open loop of these Journal of Molecular Catalysis pendant epoxies groups and addition are to form oxygen
Figure BPA0000181747600000201
functional polymer 2.The epoxy group(ing) 2 of activation can be by the side acid groups open loop of copolymer 1 b to form intermediate 3, or can be by the epoxide group open loop of copolymer 1 b to form intermediate 4.Intermediate 4 can continue cationoid polymerisation adjacent ring oxygen groups.The hydroxyl of intermediate 3 also can be used as chain-transfer agent in the cationoid polymerisation of epoxy group(ing), as J.V Crivello, D.A.Conlon, D.R.Olson " The Effects of Polyols as Chain Transfer Agents and Flexibilizers in Photoinitiated Cationic Photopolymerization ", Journal of Radiation Curing, October1986, 3-9 (J.V Crivello, D.A.Conlon, D.R.Olson, " polyvalent alcohol in light-initiated cationic photopolymerization as the effect of chain-transfer agent and toughner ", radiation curing magazine, in October, 1986, 3-9).Should be further understood that the multipolymer that (methyl) acrylate copolymer illustrating can be initial solute multipolymer or the radical polymerization of the solvent monomer that caused by secondary UV produces.
Scheme 2
Figure BPA0000181747600000211
Preferably binder composition is just coated with soon after preparation.Binder polymer composition (comprising multipolymer, monomer, epoxy resin and linking agent) as slurry is easy to be applied to suitable substrate (as flexible back lining materials) by conventional coating technique, then further polymerization curing, thereby the sheet material of preparation adhesive coated.Flexible back lining materials can be any material or any other flexible materials that is conventionally used as adhesive tape backing, blooming.
Contact adhesive composition also can comprise one or more conventional additives.Preferred additive comprises tackifier, softening agent, dyestuff, antioxidant and UV stablizer.If this class additive does not affect the premium properties of pressure sensitive adhesive, can use.
If use tackifier, the dry weight basis based on whole binder polymers, the highest 50 % by weight, are preferably less than 30 % by weight, and being more preferably less than 5 % by weight will be suitable.In certain embodiments, do not use tackifier.The suitable tackifier that use together with (methyl) acrylic ester polymer dispersion comprise sylvic acid, rosin ester, terpene phenolic resin, hydrocarbon resin and cumarone indene resin.The kind of tackifier and amount may affect such as can contact, character bonding scope, bond strength, heat impedance and specific strength.
Can prepare adhesive article by the upper coating adhesive of the carrier suitable (as flexible backing) or pre-binder composition.The example of the material that can comprise in flexible backing comprises polyolefine, polystyrene, polyester, polyvinyl alcohol, poly-(ethylene glycol terephthalate), poly-(mutual-phenenyl two acid bromide two alcohol ester), poly-(hexanolactam), poly-(vinylidene fluoride), polylactide, rhodia and the ethyl cellulose etc. such as polyethylene, polypropylene (comprising isotatic polypropylene).Can be used for the polyester film that commercially available back lining materials of the present invention comprises that HOSTAPHAN3SAB primes and (can derive from (the Mitsubishi Polyester Film Inc. of polyester film company of Mitsubishi of South Carolina Greer, Greer, SC)), kraft paper (can derive from Na Denuoke papermaking in Meng company (Monadnock Paper, Inc.)); Glassine paper (can derive from not Rec Sai Er company (Flexel Corp.)); Spunbond poly-(ethene) and poly-(propylene), for example TYVEK and TYPAR (can derive from E.I.Du Pont Company (DuPont, Inc.)); And the porous-film obtaining from poly-(ethene) and poly-(propylene), for example TESLIN (can derive from PPG Industries Inc. (PPG Industries, Inc.)) and CELLGUARD (can derive from Hirst-Celanese (Hoechst-Celanese)).
Prepared by backing also available fabric (such as by the weaven goods synthesizing or the line of natural materials forms, such as cotton, nylon, artificial silk, glass, stupalith etc.) or supatex fabric (for example gas spun web of natural fiber, synthon or their blend).Backing also can be made by metal, metallized polymeric film or ceramic sheet material, can take the shape of any goods (as label, adhesive tape, signboard, Abdeckteil, mark etc.) of common known use contact adhesive composition.
Can use the conventional coating technique that is suitable for special substrate through being improved to that above-mentioned composition is applied to substrate.For example, can these compositions be applied to many kinds of solids substrate by the method such as roller coat, flow coat, dip-coating, spin coating, spraying, blade coating and mould are coated with.Composition also can be coated with by melting.These diversified coating processes can be coated on these compositions in substrate according to different thickness, thereby these compositions are more widely used.Coat-thickness can change as described above.Paste compound can have any required concentration being coated with for subsequently, but in monomer, is the polymer solids of 5 to 20 % by weight conventionally.Can be dried to obtain required concentration by further dilution coating composition or by part.
Flexible strutting piece also can comprise exfoliated coat substrates.When adhesive transfer adhesive tape is provided, conventionally adopt this type of substrate.The example of exfoliated coat substrates is well known in the art, and comprises such as silicone coated kraft paper etc.Adhesive tape of the present invention also can mix low adhesive power backing known in the art (LAB).
example
By following instance, further illustrate objects and advantages of the present invention, but the concrete material of enumerating and amount thereof and other condition and details should not be understood as to improper restriction of the present invention in these examples.
As used herein, " pph " refers to the umber in the monomer of each hundred parts epoxy functionalized (methyl) acrylic copolymer.
testing method
peel off bonding strength test [ASTM D3330/D3330M-04]
This thermometrically with the angle of 180 degree from the required power of glass stripping tape.Use the operation of describing in the ASTM testing method of quoting, the adhesive tape of the conciliation making in example is tested.Binder formulation to be tested is applied to Mitsubishi Hostaphan tMon the polyester film of priming.By the wide adhesive tape of 12.7-millimeter (12.7-mm) is adhered to sheet glass, and prepare test sample for twice with 2-kilogram of (2-kg) roller roll extrusion on adhesive tape.Peel off with shearing test before, adhesive tape is regulated to 24 hours in controlled environment chamber (23 ℃/50% relative humidity).Platen speeds test tape on tension tester with 12 inch per minute clocks (305 mm/min (mm/min)).The data of report are three arithmetical av of measuring.Mean value represents with newton/decimetre (N/dm).
shearing resistance test [ASTM D-3654/D3654M06]
This thermometrically from one end of adhesive tape, adhere to stainless steel plate, vertically hang, and counterweight rises while being attached to the free end of adhesive tape, in the static shear intensity of the lower adhesive tape of high temperature (70 ℃).
70 ℃ of shearings: by the adhesive tape preparation test sample of the conciliation of preparing in example.By 12.7-mm wide * the long adhesive tape of 25.4-mm is attached to an edge of stainless steel plate, makes it and the overlapping 12.7mm of panel, and the roller of 2-kg is attached in the part of panel roll extrusion twice at adhesive tape.0.5-kg counterweight is attached to the free end of adhesive tape, and panel is vertically hung in the baking oven being set at 70 ℃.Measure the time that adhesive tape falls down from panel (in minute), record out-of-service time and failure mode.Failure mode can be wherein the adhesive power (a) that totally pulls off tackiness agent from panel or adhesive tape backing, or wherein tackiness agent division and part tackiness agent is stayed on adhesive tape and part is stayed the force of cohesion (c) on adhesive tape backing.If do not lost efficacy in 10,000 minutes, stop test, and record result.The data of report are three arithmetical av of measuring.
table 1: the starting material for these examples are described in following table.
Figure BPA0000181747600000241
Figure BPA0000181747600000251
the preparation of the basic slurry multipolymer that comprises epoxy acrylate comonomer
Isooctyl acrylate monomer (the IOA that packs 89g in the wide-necked bottle of 1 quart into, 89 parts), the vinylformic acid (AA of 10g, 10 parts), the vinylformic acid 4-hydroxyl butyl ester glycidyl ether (4-HBAGE, 1 part) of 1g and the Irgacure of 0.04g (0.04phr) tM651.Monomer mixture is used to nitrogen purging 5 minutes, be then exposed to low-intensity ultraviolet radiation, until preparation can application type slurry multipolymer.
By the Irgacure of pre-binder polymer slurry and extra 0.16g (0.16phr) tM651 blend and with two (4-tert-butyl-phenyl) iodine of 0.2g (0.2phr)
Figure BPA0000181747600000252
hexafluoro antimonate (Hampford) blend, as shown in table 2.
the compounding of the final slurry that comprises epoxy resin:
In the bottle of 25 dram, pack the basic slurry from the preparation A in table 2 of 20g (100phr) and the Epon-828 of 0.2g (1phr) into the example 2 in preparation table 3.Every other sample is by using the resin concentration of different epoxy resin and variation to be prepared in a similar fashion, as shown in table 3-4.Then for the pre-binder formulation of slurry, at Mitsubishi Hostaphan tMon the polyester film of priming, be coated with the thick preparation of 2 mils (approximately 50 microns), and by long wave ultraviolet (550mJ/cm 2) be cured.
the compounding of the final slurry that comprises epoxy resin and tackifier:
In the bottle of 25 dram, pack the Epon-828 of the basic slurry from the preparation A in table 2 of 20g (100phr), the Foral85LB of 1.0g (10phr) and 0.2g (1phr) into the example 9 in preparation table 5.Every other sample is prepared in a similar fashion by using the resin concentration of different epoxy resin, variation and using various tackifier to fill, as shown in table 5-6.Then for the pre-binder formulation of slurry, at Mitsubishi Hostaphan tMon the polyester film of priming, be coated with the thick preparation of 2 mils (approximately 50 microns), and by long wave ultraviolet (550mJ/cm 2) be cured.
preparation for the slurry of the IOA/AA control sample that comprises optional tackifier
In the wide-necked bottle of 1 quart, pack the Isooctyl acrylate monomer (IOA, 90 parts) of 45g, the vinylformic acid (AA, 10 parts) of 5g and the Irgacure of 0.02g (0.04phr) into tM651.By nitrogen purging 5 minutes for monomer mixture, be then exposed to low-intensity ultraviolet radiation, can application type slurry multipolymer until make, then add the Irgacure of extra 0.08g (0.16phr) tM651, the Foral85LB tackifier of the HDDA of 0.04g (0.08phr) and optional 5g (10phr), as shown in table 7.Then for the pre-binder formulation of slurry, at Mitsubishi Hostaphan tMon the polyester film of priming, be coated with the thick preparation of 2 mils (approximately 50 microns), then by long wave ultraviolet (550mJ/cm 2) be cured.
Described in above testing method, for the adhesive tape of being prepared by these tackiness agents, measure peel adhesion and shearing resistance.
table 2: comprise two (4-tert-butyl-phenyl) iodine
Figure BPA0000181747600000262
hexafluoro antimonate (Hampford) and vinylformic acid the composition of the preparation of the basic slurry of 4-hydroxyl butyl ester glycidyl ether (4-HBAGE).
Figure BPA0000181747600000261
table 3: in the Epon-828 and the table 2 with UVA Radiation that comprises various content the binder formulation of preparation A basis slurry.
Figure BPA0000181747600000271
table 4: in the ERL-4221 and the table 2 with UVA Radiation that comprises various content the binder formulation of preparation A basis slurry.
Figure BPA0000181747600000272
table 5: the Epon-828 that comprises tackifier Foral85LB, various content or ERL-4221 and the binder formulation with the basic slurry in the table 2 of UVA Radiation.
Figure BPA0000181747600000281
The cohesive mode that c representative was lost efficacy.
table 6: tackifier Foral85LB, the Epon-828 or the ERL-4221 that comprise various content and the binder formulation with the basic slurry in the table 2 of UVA Radiation.
Figure BPA0000181747600000282
The cohesive mode that c representative was lost efficacy.
table 7: comprise HDDA and optional Foral85LB tackifier but do not comprise epoxy monomer or the control formulation of salt.
Figure BPA0000181747600000291
The cohesive mode that c representative was lost efficacy.
Following examples further illustrate the present invention:
1. a crosslinkable slurry polymerisation compositions, comprises:
A) epoxy functionalized (methyl) vinylformic acid solute multipolymer that comprises mutually poly-monomer, described mutually poly-monomer comprises:
I) (methyl) alkyl acrylate monomer;
Ii) epoxy functionalized (methyl) acryloyl monomer;
Iii) optional sour official's energy ethylenically unsaturated monomers;
Iv) optional non-sour official's energy polar monomer;
V) optional vinyl monomer, and
Vi) optional multifunctional (methyl) acrylate cross linked dose;
B) epoxy resin; With
C) ionic light acid producing agent
D) solvent monomer mixture, described solvent monomer mixture comprises:
I) (methyl) alkyl acrylate monomer;
Ii) epoxy functionalized (methyl) acryloyl monomer
Iii) optional sour official's energy ethylenically unsaturated monomers;
Iv) optional non-sour official's energy polar monomer;
V) optional vinyl monomer, and
Vi) optional multifunctional (methyl) acrylate cross linked dose.
2. according to the crosslinkable slurry polymerisation compositions described in embodiment 1, wherein said ionic light acid producing agent is used with the amount of epoxy functionalized multipolymer 0.01 to 1 weight part with respect to 100 weight parts.
3. according to the crosslinkable slurry polymerisation compositions described in any one in embodiment 1 or 2, epoxy functionalized (methyl) acryloyl monomer of wherein said solute multipolymer is used with the amount of total monomer 1 to 20 weight part of the epoxy functionalized multipolymer with respect to 100 weight parts.
4. according to the crosslinkable slurry polymerisation compositions described in any one in previous embodiment, the sour official of wherein said solute multipolymer can use with the amount of 1 to 15 weight part of the total monomer of the epoxy functionalized multipolymer of 100 parts by ethylenically unsaturated monomers.
5. according to the crosslinkable slurry polymerisation compositions described in any one in previous embodiment, wherein said epoxy functionalized (methyl) vinylformic acid solute multipolymer comprises mutually poly-monomer, the total monomer content meter that described mutually poly-monomer comprises the epoxy functionalized multipolymer based on 100 parts:
I) (methyl) acrylate of the non-tertiary alcohol of 85 to 99 weight parts;
Ii) epoxy functionalized (methyl) acryloyl monomer of 1 to 20 weight part; With
Iii) optionally the sour official of 1 to 15 weight part can ethylenically unsaturated monomers.
6. according to the crosslinkable slurry polymerisation compositions described in any one in previous embodiment, wherein said epoxy functionalized (methyl) acryloyl monomer is used in the amount of epoxy functionalized multipolymer 1 to 10 weight part based on 100 parts.
7. according to the crosslinkable slurry polymerisation compositions described in any one in previous embodiment, wherein said (methyl) acrylic copolymer also comprises mutually poly-monomer, and described mutually poly-monomer comprises that non-sour official can polar monomer and vinyl monomer.
8. according to the crosslinkable slurry polymerisation compositions described in any one in embodiment 1 to 7, also comprise multifunctional (methyl) acrylate monomer.
9. according to the crosslinkable slurry polymerisation compositions described in any one in embodiment 1 to 8, wherein said ionic light acid producing agent is selected from iodine
Figure BPA0000181747600000314
salt; Sulphur salt, sulfur oxide
Figure BPA0000181747600000316
salt, selenium
Figure BPA0000181747600000317
salt, sulfur oxide
Figure BPA0000181747600000318
salt,
Figure BPA0000181747600000319
salt and arsenic
Figure BPA00001817476000003110
salt.
10. according to the crosslinkable slurry polymerisation compositions described in embodiment 9, wherein said salt is selected from SbF 6 -, AsF 6 -, PF 6 -, B (C 6f 5) 4 -and BF 4 -and B (C 6f 5) 4 -negatively charged ion.
11. according to the crosslinkable slurry polymerisation compositions described in any one in embodiment 1 to 10, and wherein said epoxy functionalized (methyl) acryloyl monomer has following formula:
Wherein:
R 7for-H or C 1-C 4alkyl;
X 1for-O-or-NR 9-;
R 8hydrocarbyl group for epoxy group(ing) replacement; And
R 9for-H or C 1-C 4alkyl.
12. according to the crosslinkable slurry polymerisation compositions described in embodiment 11, wherein R 8for
Figure BPA0000181747600000312
R wherein 4for C 1-C 6alkylidene group.
13. according to the crosslinkable slurry polymerisation compositions described in any one in embodiment 1 to 10, and wherein said epoxy functionalized (methyl) acryloyl monomer has following formula:
Figure BPA0000181747600000313
Wherein:
R 10for (mixing) hydrocarbyl group;
R 11for-H or-H or C 1-C 4alkyl;
X 2for-NR 12-or-O-; And
R 12for-H or C 1-C 4alkyl.
14. according to the crosslinkable slurry polymerisation compositions described in embodiment 1, and described crosslinkable slurry polymerisation compositions comprises:
A) the epoxy functionalized solute multipolymer that comprises mutually poly-monomer, described mutually poly-monomer comprises:
I) (methyl) acrylate monomer of 85 to 99 weight parts;
Ii) epoxy functionalized (methyl) acryloyl monomer of 1 to 20 weight part;
Iii) sour official's energy ethylenically unsaturated monomers of 0 to 15 weight part;
Iv) non-sour official's energy polar monomer of 0 to 10 weight part;
V) vinyl monomer of 0 to 5 weight part;
Vi) multifunctional (methyl) acrylate cross linked dose of 0 to 5 part;
B) epoxy resin and
C) the epoxy functionalized multipolymer based on 100 weight parts a) is counted, the ionic light acid producing agent of 0.01 to 1 weight part.
15. according to the crosslinkable slurry polymerisation compositions described in any one in embodiment 1 to 14, also comprises tackifier.
16. according to the crosslinkable slurry polymerisation compositions described in any one in embodiment 1 to 10, and wherein said epoxy functionalized (methyl) acryloyl monomer has following formula:
Figure BPA0000181747600000321
R wherein 4for C 1-C 4alkylidene group.
17. according to the crosslinkable slurry polymerisation compositions described in any one in previous embodiment, and wherein said epoxy resin is the glycidyl ether with following formula:
Figure BPA0000181747600000331
Wherein
R 1for (mixing) hydrocarbyl group, and m is 1 to 6.
18. according to the crosslinkable slurry polymerisation compositions described in any one in previous embodiment, comprises the epoxy resin with respect to epoxy functionalized multipolymer 0.1 to 10 weight part of 100 weight parts.
19. 1 kinds of contact adhesive compositions, prepared by the cross-linkable composition of its any one in embodiment 1 to 16.
20. 1 kinds of pressure-sensitive adhesive articles, are included in the coating of the tackiness agent of the embodiment 19 on backing.
21. 1 kinds of methods of preparing pressure sensitive adhesive, comprise the following steps
A) provide slurry copolymer compositions, the solute multipolymer that described slurry copolymer compositions comprises solvent monomer, light trigger and following mutually poly-monomeric unit:
I) (methyl) alkyl acrylate monomer;
Ii) epoxy functionalized (methyl) acryloyl monomer;
Iii) optional sour official's energy ethylenically unsaturated monomers;
Iv) optional non-sour official's energy polar monomer;
V) optional vinyl monomer; And
B) described slurry copolymer compositions and epoxy resin and ionic light acid producing agent, optional multifunctional (methyl) acrylate and optional additional optical initiator are mixed, and
C) by ultraviolet radiation, irradiate.

Claims (21)

1. a crosslinkable slurry polymerisation compositions, comprises:
A) epoxy functionalized (methyl) vinylformic acid solute multipolymer that comprises mutually poly-monomer, described mutually poly-monomer comprises:
I) (methyl) alkyl acrylate monomer;
Ii) epoxy functionalized (methyl) acryloyl monomer;
Iii) optional sour official's energy ethylenically unsaturated monomers;
Iv) optional non-sour official's energy polar monomer;
V) optional vinyl monomer, and
Vi) optional multifunctional (methyl) acrylate cross linked dose;
B) epoxy resin; With
C) ionic light acid producing agent
D) solvent monomer mixture, described solvent monomer mixture comprises:
I) (methyl) alkyl acrylate monomer;
Ii) epoxy functionalized (methyl) acryloyl monomer
Iii) optional sour official's energy ethylenically unsaturated monomers;
Iv) optional non-sour official's energy polar monomer;
V) optional vinyl monomer, and
Vi) optional multifunctional (methyl) acrylate cross linked dose.
2. crosslinkable slurry polymerisation compositions according to claim 1, wherein said ionic light acid producing agent is used with the amount of described epoxy functionalized multipolymer 0.01 to 1 weight part with respect to 100 weight parts.
3. according to the crosslinkable slurry polymerisation compositions described in any one in claim 1, described epoxy functionalized (methyl) acryloyl monomer of wherein said solute multipolymer is used with the amount of total monomer 1 to 20 weight part of the described epoxy functionalized multipolymer with respect to 100 weight parts.
4. crosslinkable slurry polymerisation compositions according to claim 1, the described sour official of wherein said solute multipolymer can use with the amount of 1 to 15 weight part of the total monomer of the described epoxy functionalized multipolymer of described 100 parts by ethylenically unsaturated monomers.
5. crosslinkable slurry polymerisation compositions according to claim 1, wherein said epoxy functionalized (methyl) vinylformic acid solute multipolymer comprises mutually poly-monomer, and described mutually poly-monomer comprises the total monomer content meter of the described epoxy functionalized multipolymer based on 100 parts:
I) (methyl) acrylate of the non-tertiary alcohol of 85 to 99 weight parts;
Ii) epoxy functionalized (methyl) acryloyl monomer of 1 to 20 weight part; With
Iii) optionally the sour official of 1 to 15 weight part can ethylenically unsaturated monomers.
6. crosslinkable slurry polymerisation compositions according to claim 1, wherein said epoxy functionalized (methyl) acryloyl monomer is used in the amount of described epoxy functionalized multipolymer 1 to 10 weight part based on 100 parts.
7. crosslinkable slurry polymerisation compositions according to claim 1, wherein said (methyl) acrylic copolymer also comprises mutually poly-monomer, and described mutually poly-monomer comprises that non-sour official can polar monomer and vinyl monomer.
8. crosslinkable slurry polymerisation compositions according to claim 1, also comprises multifunctional (methyl) acrylate monomer.
9. crosslinkable slurry polymerisation compositions according to claim 1, wherein said ionic light acid producing agent is selected from iodine salt; Sulphur
Figure FPA0000181747590000023
salt, sulfur oxide salt, selenium
Figure FPA0000181747590000025
salt, sulfur oxide
Figure FPA0000181747590000026
salt,
Figure FPA0000181747590000027
salt and arsenic
Figure FPA0000181747590000028
salt.
10. crosslinkable slurry polymerisation compositions according to claim 9, wherein said salt is selected from SbF 6 -, AsF 6 -, PF 6 -, B (C 6f 5) 4 -and BF 4 -and B (C 6f 5) 4 -negatively charged ion.
11. crosslinkable slurry polymerisation compositions according to claim 1, wherein said epoxy functionalized (methyl) acryloyl monomer has following formula:
Wherein:
R 7for-H or C 1-C 4alkyl;
X 1for-O-or-NR 9-;
R 8hydrocarbyl group for epoxy group(ing) replacement; And
R 9for-H or C 1-C 4alkyl.
12. crosslinkable slurry polymerisation compositions according to claim 11, wherein R 8for
Figure FPA0000181747590000031
R wherein 4for C 1-C 6alkylidene group.
13. according to the crosslinkable slurry polymerisation compositions described in any one in claim 1, and wherein said epoxy functionalized (methyl) acryloyl monomer has following formula:
Figure FPA0000181747590000032
Wherein:
R 10for (mixing) hydrocarbyl group;
R 11for-H or-H or C 1-C 4alkyl;
X 2for-NR 12-or-O-; And
R 12for-H or C 1-C 4alkyl.
14. crosslinkable slurry polymerisation compositions according to claim 1, comprise:
A) the epoxy functionalized solute multipolymer that comprises mutually poly-monomer, described mutually poly-monomer comprises:
I) (methyl) acrylate monomer of 85 to 99 weight parts;
Ii) epoxy functionalized (methyl) acryloyl monomer of 1 to 20 weight part;
Iii) sour official's energy ethylenically unsaturated monomers of 0 to 15 weight part;
Iv) non-sour official's energy polar monomer of 0 to 10 weight part;
V) vinyl monomer of 0 to 5 weight part;
Vi) multifunctional (methyl) acrylate cross linked dose of 0 to 5 part;
B) epoxy resin and
C) the described epoxy functionalized multipolymer based on 100 weight parts a) is counted, the ionic light acid producing agent of 0.01 to 1 weight part.
15. crosslinkable slurry polymerisation compositions according to claim 1, also comprise tackifier.
16. crosslinkable slurry polymerisation compositions according to claim 1, wherein said epoxy functionalized (methyl) acryloyl monomer has following formula:
Figure FPA0000181747590000041
R wherein 4for C 1-C 4alkylidene group.
17. crosslinkable slurry polymerisation compositions according to claim 1, wherein said epoxy resin is the glycidyl ether with following formula:
Figure FPA0000181747590000042
Wherein
R 1for (mixing) hydrocarbyl group, and m is 1 to 6.
18. crosslinkable slurry polymerisation compositions according to claim 1, comprise the described epoxy resin with respect to described epoxy functionalized multipolymer 0.1 to 10 weight part of 100 weight parts.
19. 1 kinds of contact adhesive compositions, it is prepared by cross-linkable composition claimed in claim 1.
20. 1 kinds of pressure-sensitive adhesive articles, are included in the coating of the tackiness agent described in the claim 19 on backing.
21. 1 kinds of methods of preparing pressure sensitive adhesive, comprise the following steps:
A) provide slurry copolymer compositions, the solute multipolymer that described slurry copolymer compositions comprises solvent monomer, light trigger and following mutually poly-monomeric unit:
I) (methyl) alkyl acrylate monomer;
Ii) epoxy functionalized (methyl) acryloyl monomer;
Iii) optional sour official's energy ethylenically unsaturated monomers;
Iv) optional non-sour official's energy polar monomer;
Vi) optional vinyl monomer; And
B) described slurry copolymer compositions and epoxy resin and ionic light acid producing agent, optional multifunctional (methyl) acrylate and optional additional optical initiator are mixed, and
C) by ultraviolet radiation, irradiate.
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